Non-aqueous electrolyte secondary battery

ABSTRACT

A non-aqueous electrolyte secondary battery is provided, including a battery element having a positive electrode, a negative electrode and a separator; an exterior member for the battery element including: a first layer; a second layer; a bending part for partitioning the first layer and the second layer from each other; a sealing part which is formed by a peripheral part of the first layer in contact with a peripheral part of the second layer and which seals the battery element; a thick-walled part that is a portion of the sealing part and includes at least a part of the bending part, wherein the thick-walled part has a greater thickness in a thickness direction of the battery element than a thickness of a portion of the sealing part other than the thick-walled part, and wherein the thickness direction of the battery element corresponds to a stacking direction of the battery element.

CROSS REFERENCES TO RELATED APPLICATIONS

The present application is a continuation of U.S. patent applicationSer. No. 12/474,832, filed on May 29, 2009, which claims priority toJapanese Priority Patent Application JP 2008-144781 filed in JapanPatent Office on Jun. 2, 2008, the entire contents of which is herebyincorporated by reference.

BACKGROUND

The present application relates to an exterior member for a batteryelement for packaging a battery element and to a non-aqueous electrolytesecondary battery using the same. In more detail, the presentapplication relates to an exterior member for a battery element capableof reducing failures, for example, leakage of the contents of a batteryand swelling of a battery to be caused due to moisture absorption fromthe outside of the battery, through an enhancement of hermetic sealingproperties, and to a non-aqueous electrolyte secondary battery using thesame.

In recent years, a number of portable electronic devices, for example,camcorders (video tape recorders), cellular phones and laptop computers,each achieving a reduction in size and weight, have appeared. Followingthis, a demand for batteries as a power source of portable electronicdevices is rapidly increasing. In order to realize a reduction in sizeand weight of the device, it is demanded to design the battery such thatthe battery is lightweight and thin and that a housing space within thedevice can be efficiently used. As a battery capable of meeting suchdemands, a lithium ion battery with a large energy density and a largeoutput density is the most favorable.

Above all, a battery with a high degree of freedom in shape, a sheettype battery with a thin large area, a card type battery with a thinsmall area and the like have been desired. However, it is difficult toprepare a thin battery according to techniques using a metal-made can asan exterior material, which have hitherto been employed.

In order to solve these problems, there are investigated batteries notcontaining a liquid electrolyte therein, by adding a material having asolidification action to an electrolytic solution or using a gelelectrolyte using a polymer. In such batteries, an electrode and anelectrolyte are brought into intimate contact with each other, and it ispossible to keep the contact state. According to this, it is possible toprepare a thin battery using an exterior member in a sheet form, such asan aluminum laminated sheet.

FIG. 9 shows an exploded perspective view of the foregoing thin batteryusing a laminated sheet as an exterior member. This laminated battery 10is configured such that a battery element 20 is externally packaged inan exterior member 30 for a battery element made of a laminated sheet.

Here, the exterior member 30 for a battery element is formed such that arecess-provided sheet piece 30A having a recess 20 for housing thebattery element 20 in a rectangular plate form and a platy sheet piece30B in a platy form are partitioned from each other by a bending part34. The laminated battery 10 is prepared by housing the battery element20 in the recess 32 of the recess-provided sheet piece 30A, foldingdouble the recess-provided sheet piece 30A and the platy sheet piece 30Bin the bending part 34 and then sealing a peripheral part 36 of the bothsheet pieces under a heat pressure.

The foregoing bending part of the laminated sheet is bent at about 360°C. during sealing and further applied with a load of the heat pressure.Thus, the bending part of the laminated sheet is easily damaged at thetime of sealing as compared with other peripheral part (sealing part).Nevertheless, according to the related art, since a sealing region(peripheral part width) of the laminated sheet was sufficiently secured,even when the foregoing load would be applied, the damage was rarelyactualized. However, in recent years, following an increase of thebattery capacity, not only the sealing region is made narrow to aminimum width, but in order to compensate this, there is a tendency thatsealing is carried out at high temperature and high pressure.Accordingly, the foregoing bending part forms a place where delaminationor a pinhole which will become a factor of lowering the hermetic sealingproperties is easily generated. Thus, it is the present situation thatthere is a concern that a lowering of the hermetic sealing properties ofthe thin laminated battery is generated.

On the other hand, there is disclosed a method in which one of externalends of a laminated exterior body is extended to provide an extendedend, and the other external end is covered by the extended end, therebyenhancing hermetic sealing properties (see JP-A-2003-242942).

SUMMARY

However, according to the method disclosed in JP-A-2003-242942, thenumber of the bending part of the laminated sheet increases, andlaminated sheet processing is complicated. Thus, the number ofmanufacturing steps increases, resulting in complicatedness.

In view of the foregoing problems of the related art, it is desirable toprovide an exterior member for a battery element which is able torealize excellent hermetic sealing properties and to contribute torealization of a high capacity without increasing the number ofmanufacturing steps of a battery and to provide a non-aqueouselectrolyte secondary battery using the same.

The present inventors have conducted investigations, and as a result, ithas been found that with respect to a laminated sheet for forming anexterior member for a battery element, the foregoing desire can beachieved by providing a thick-walled part in at least a part of abending part in accordance with an embodiment of the presentapplication.

According to an embodiment, there is provided an exterior member for abattery element including:

a first sheet piece made of a laminated sheet;

a second sheet piece made of a laminated sheet;

a bending part for partitioning the first sheet piece and the secondsheet piece from each other;

a sealing part which is formed by a peripheral part of the first sheetpiece and a peripheral part of the second sheet piece corresponding tothe peripheral part of the first sheet piece and which hermeticallyseals a battery element; and

a thick-walled part formed so as to include at least a part of thebending part.

According to another embodiment, there is provided a non-aqueouselectrolyte secondary battery including:

a battery element in a rectangular plate form having a positiveelectrode and a negative electrode wound therein via a separator; and

an exterior member for a battery element including

a first sheet piece made of a laminated sheet;

a second sheet piece made of a laminated sheet;

a bending part for partitioning the first sheet piece and the secondsheet piece from each other;

a sealing part which is formed by a peripheral part of the first sheetpiece and a peripheral part of the second sheet piece corresponding tothe peripheral part of the first sheet piece and which hermeticallyseals a battery element; and

a thick-walled part formed so as to include at least a part of thebending part.

According to an embodiment, by providing a thick-walled part in at leasta part of a bending part with respect to an exterior member for abattery element made of a laminated sheet, it is possible to provide anexterior member for a battery element which is able to realize excellenthermetic sealing properties and to contribute to realization of a highcapacity without increasing the number of manufacturing steps of abattery; and to provide a non-aqueous electrolyte secondary batteryusing the same.

Additional features and advantages are described in, and will beapparent from, the following Detailed Description and the figures.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a plan view showing the state that a battery element is housedin an exterior member for a battery element according to an embodiment.

FIGS. 2A, 2B and 2C are plan views each showing the state that a batteryelement is housed in an exterior member for a battery element accordingto another embodiment.

FIGS. 3A, 3B and 3C are side views each showing the state that a batteryelement is housed in an exterior member for a battery element accordingto another embodiment.

FIG. 4 is a side view showing the state that a battery element is housedin an exterior member for a battery element according to yet anotherembodiment.

FIGS. 5A, 5B and 5C are schematic views each showing a manufacturingmethod of an exterior member for a battery element of the related artand that according to an embodiment.

FIG. 6 is a perspective view showing a heater bar to be used for themanufacture of an exterior member for a battery element according to anembodiment.

FIG. 7 is an exploded perspective view showing a non-aqueous electrolytesecondary battery according to an embodiment.

FIG. 8 is a schematic cross-sectional view along a VIII-VIII line of thebattery element shown in FIG. 7.

FIG. 9 is an exploded perspective view of a related-art thin batteryusing a laminated sheet as an exterior member.

DETAILED DESCRIPTION

An exterior member for a battery element and a non-aqueous electrolytesecondary battery according to an embodiment of the present applicationwill be described in detail with reference to the accompanying drawings.

(1) Exterior Member for Battery Element

FIG. 1 is a plan view showing the state that a battery element is housedin an exterior member for a battery element according to an embodiment.

In FIG. 1, in this exterior member 300 for a battery element, arecess-provided sheet piece 300A made of a laminated sheet, which is oneexample of a first sheet piece, and a platy sheet piece 300B made of alaminated sheet, which is one example of a second sheet piece, areformed partitioned by a bending part 34, and a thick-walled part 40 isprovided so as to include at least a part of the bending part 34.

A non-aqueous electrolyte battery 100 provided with this exterior member30 for a battery element is prepared by housing a battery element 20 ina recess 32 of the recess-provided sheet piece 300A while leading out aterminal 22 and a sealant 24 of the battery element 20 externally,subsequently folding the platy sheet piece 300B in the bending part 34to superimpose the both sheet pieces 300A and 300B and heat sealingperipheral parts 36A and 36B of the both sheet pieces (the peripheralparts of the both sheet pieces will be hereinafter sometimes referred tosimply as “peripheral part 36”) to form a sealing part 38.

In the present embodiment, though the recess for housing a batteryelement is provided only in the first sheet piece, the form of each ofthe first sheet piece and the second sheet piece is not limited so faras it is able to house the battery element therein. For example, (1) aform in which each of the first sheet piece and the second sheet piecehas a recess which forms a half of a battery element-housing part; (2) aform in which only the second sheet piece has a recess for housing thebattery element therein; (3) a platy form in which both the first sheetpiece and the second sheet piece do not have a recess, and the batteryelement can be housed while interposing it by the both sheet pieces; andthe like can be adopted.

Though the thick-walled part 40 is formed under a heat pressingsimultaneously with heat sealing for forming the sealing part 38 in theperipheral part 36 in which the bending part 34 is included, it ispreferable that the thick-walled part 40 is formed by a pressure lowerthan a pressure the sealing part 38 is formed by. The thick-walled part40 is able to relieve a damage from which the bending part 34 suffersduring this heat sealing and to significantly suppress the generation ofdelamination or a pinhole in the bending part 34 or in the vicinitythereof.

Accordingly, the non-aqueous electrolyte battery of the presentembodiment having the foregoing configuration and having enhancedsealing properties hardly generates failures, for example, leakage ofthe contents of a battery and swelling of a battery to be caused due tomoisture absorption from the outside of the battery.

Though the thickness of the thick-walled part 40 may be uniform ornon-uniform, the thickness of a thickest portion thereof is preferablyfrom 1.2 to 3 times, and more preferably from 1.2 to 2 times thethickness of the sealing part 38 where no thick-walled part is formed.

This is because when the thickness of the thick-walled part 40 is lessthan 1.2 times, there may be the case where an effect for reducing thedamage at the time of heat sealing is not obtained, whereas when itexceeds 3 times, there may be the case where the sealing part becomesthick so that the penetration amount of moisture increases, leading to afactor of swelling of the battery.

Also, a length (T) in the long side direction of the thick-walled part40, namely the length of the thick-walled part 40 formed in theterminal-leading direction from the bending part 34, is preferably notmore than 80% relative to a length (S) of the long side of the exteriormember 30 for a battery element, namely the length in the lead-outdirection of the terminal 22. It is preferable that this proportion issmall as far as possible. This is because in a portion where thethickness of the sealing part 38 formed in the exterior member for abattery element is thick, the penetration amount of moisture increases,leading to a factor of swelling of the battery, and therefore, when thesubject proportion exceeds 80%, a risk of the generation of swelling ofthe battery increases. Also, this is because the volume of the whole ofthe battery increases in vain, resulting in going against therealization of a high capacity of the battery.

FIGS. 2A, 2B and 2C are plan views each showing the state that a batteryelement is housed in an exterior member for a battery element accordingto another embodiments, respectively.

As shown in these three embodiments, the thick-walled part 40 does notnecessarily extend over the whole width of the bending part 34 but mayinclude at least a part thereof. Also, as to the shape of thethick-walled part 40, it can be formed in an arbitrary shape in terms ofa planar shape thereof, such as a semicircular shape, a triangular shapeand a polygonal shape, in addition to a rectangular shape as shown inFIGS. 2A, 2B and 2C.

FIGS. 3A, 3B and 3C are side views each showing the state that a batteryelement is housed in an exterior member for a battery element accordingto still another embodiment.

As shown in these three embodiments, the thick-walled part 40 can take aform in which it is protruded in an arbitrary direction. Examples ofsuch a form include a form in which the thick-walled part 40 isprotruded on the side having the recess 32 for housing a battery elementtherein (FIG. 3A); a form in which the thick-walled part 40 is protrudedon the opposite side thereto (FIG. 3B); and a form in which thethick-walled part 40 is protruded on the both sides (FIG. 3C).

FIG. 4 is a side view showing the state that a battery element is housedin an exterior member for a battery element according to an even stillanother embodiment.

The thick-walled part 40 may have a level difference from the sealingpart 38 as in the previously shown embodiments shown in FIGS. 3A to 3Cor may have an inclination relative to the sealing part 38 as in theembodiment shown in FIG. 4. Also, the slope of forming an inclination isnot necessarily a smooth face but may be, for example, a curved face.

The laminated sheet which forms each of the recess-provided sheet piece300A and the platy sheet piece 300B is, for example, a rectangular sheetobtained by sticking a nylon film, an aluminum foil and a polyethylenefilm in this order. The laminated sheet is sealed by, for example,folding double it in the bending part such that the polyethylene filmside faces toward the inside and sealing the peripheral part 36A of therecess-provided sheet piece 300A and the peripheral part 36B of theplaty sheet piece 300B as superimposed each other through heat sealing.

Also, for the purpose of preventing penetration of the air, it ispreferable that the sealant 24 is inserted between the laminated sheetand each of the positive electrode and negative electrode terminals 22as shown in FIG. 1. The sealant 24 is constituted of a material havingadhesion to each of the positive electrode and negative electrodeterminals 22. For example, when such terminals are each constituted of ametal material, it is preferable that the sealant 24 is constituted of apolyolefin resin such as polyethylene, polypropylene, modifiedpolyethylene and modified polypropylene.

A general configuration of the laminated sheet can be expressed by alaminate structure of exterior layer/metal foil/sealant layer (however,the exterior layer and the sealant layer are sometimes configured ofplural layers). In the foregoing example, the nylon film iscorresponding to the exterior layer, the aluminum foil is correspondingto the metal foil, and the polyethylene film is corresponding to thesealant layer.

It is sufficient that the metal foil functions as a barrier membranehaving water vapor permeation resistance. As the metal foil, not onlythe aluminum foil but a stainless steel foil, a nickel foil and a platediron foil are useful. Of these, the aluminum foil which is thin andlightweight and is excellent in workability can be favorably used.

Examples of a mode of the configuration (exterior layer/metalfoil/sealant layer) which can be used as the laminated sheet to be usedas the exterior member for a battery element according to an embodimentinclude Ny (nylon)/Al (aluminum)/CPP (cast polypropylene), PET(polyethylene terephthalate)/Al/CPP, PET/Al/PET/CPP, PET/Ny/Al/CPP,PET/Ny/Al/Ny/CPP, PET/Ny/Al/Ny/PE (polyethylene), Ny/PE/Al/LLDPE (linearlow density polyethylene), PET/PE/Al/PET/LDPE (low density polyethylene)and PET/Ny/Al/LDPE/CPP. However, it should be understood that thepresent application is not limited to the above-referenced examples.

The exterior member for a battery element according to an embodiment mayalso be constituted of a laminated sheet having other structure, forexample, a metal material-free laminated sheet, in place of theforegoing laminated sheet.

Next, a method for manufacturing an exterior member for a batteryelement according to an embodiment is described with reference to FIGS.5A, 5B and 5C. In FIGS. 5A, 5B and 5C, though there may be the casewhere each laminated sheet has a recess for housing a battery elementtherein, illustration is omitted.

Heretofore, as shown in FIGS. 5A and 5B, an exterior member for abattery element was manufactured by heat sealing two laminated sheets 31a or a double-folded laminated sheet 31 b using a pair of heater bars500 a and 500 b in a platy shape.

Specifically, first of all, the two laminated sheets 31 a or thedouble-folded laminated sheet 31 b which will be a material is disposedbetween a pair of the heated heater bars 500 a and 500 b, or between theheated heater bar 500 a (or 500 b) and the non-heated other heater bar500 b (or 500 a), such that the respective adhesive layers of thelaminated sheet or sheets face inward (see FIG. 5A-(I) and FIG. 5B-(I)).Subsequently, the laminated sheet or sheets are interposed by the heaterbars 500 a and 500 b and heat pressed to form a sealing part (see FIG.5A-(II) and FIG. 5B-(II)), thereby obtaining the exterior member for abattery element (see FIG. 5A-(III) and FIG. 5B-(III)).

On the other hand, in the manufacture of an exterior member for abattery element according to an embodiment, for example, a leveldifference-provided heater bar 500 c and a heater bar 500 d in a platyshape as shown in FIG. 5C can be used in place of the related-art pairof heater bars in a platy shape.

The level difference-provided heater bar 500 c is provided with a leveldifference portion 501 such that a degree of heat pressure applied to aportion where the thick-walled part 40 is formed, namely a portionincluding the bending part 34, is smaller than a degree of heat pressureapplied to other sealing part 38.

In the method for manufacturing an exterior member for a battery elementaccording to an embodiment, for example, a laminated sheet 31 c whichhas been folded double in the bending part 34 is first disposed betweena pair of the heated heater bars 500 c and 500 d, or between the heatedheater bar 500 c (or 500 d) and the non-heated other heater bar 500 d(or 500 c), such that the respective adhesive layers of the laminatedsheet or sheets 31 c face inward and that the bending part 34 iscorresponding to the level difference portion 501 (see FIG. 5C-(I)).

Subsequently, the laminated sheet 31 c is interposed by the heater bars500 c and 500 d (see FIG. 5C-(II)). At that time, the portion where thethickness-walled part 40 is formed is heat pressed relatively lightly,whereby the portion where the other sealing part 38 is formed is heatpressed to the same degree as in the related art. Thus, the thick-walledpart 40 having desired thickness, width and length is formed bycontrolling the shape of the level difference portion 501 and the like,thereby obtaining the exterior member for a battery element according toan embodiment (see FIG. 5C-(III)).

Also, for example, in the case where a thick-walled part including onlya part of the bending part is formed as in the embodiments as shown inFIGS. 2A, 2B and 2C, a heater bar having a shape as shown in FIG. 6 canbe used.

Furthermore, as other manufacturing method, there can be exemplified amethod in which heat sealing is carried out dividedly twice using a pairof heater bars in a platy shape, the manner of which has hitherto beenemployed.

Specifically, first of all, the whole of the portion for forming asealing part is interposed by the foregoing heater bars in a platyshape, and first heat sealing is carried out relatively weakly (at a lowtemperature under a low pressure). Subsequently, the heater bars areshifted, the laminated sheet is interposed by the heater bars whileavoiding the portion for forming a thick-walled part, and second heatsealing is carried out relatively strongly (at a high temperature undera high pressure for a long period of time). In this way, by carrying outthe heat sealing dividedly twice under different conditions, an exteriormember for a battery element having a thick-walled part formed only byheat sealing under a low-temperature and low-pressure condition isobtained.

An example of the condition which is employed in the subject method isshown in Table 1.

TABLE 1 Pressure of air to be fed Heat Temperature into heater pressingof heater bar Heater bar to be heated bar cylinder time Weak 190° C.Only one of a pair of 0.15 MPa 3 seconds condition heater bars Strong200° C. Both of a pair of heater  0.2 MPa 3 seconds condition bars

(2) Non-Aqueous Electrolyte Secondary Battery

Next, the non-aqueous electrolyte secondary battery according to anembodiment is described in detail.

FIG. 7 is an exploded perspective view showing a non-aqueous electrolytesecondary battery according to an embodiment.

In FIG. 7, this secondary battery is formed by enclosing the woundbattery element 20 installed with a positive electrode terminal 22 a anda negative electrode terminal 22 b in the recess 32 of the exteriormember 300 for a battery element having a configuration such that therecess-provided sheet piece 300A which is one example of the first sheetpiece and the platy sheet piece 300B which is one example of the secondsheet piece are partitioned from each other by the bending part 34.Also, the positive electrode terminal 22 a and the negative electrodeterminal 22 b are each led out in, for example, the same direction fromthe inside to the outside of the exterior member 300 for a batteryelement. The positive electrode terminal 22 a and the negative electrodeterminal 22 b are each constituted of a metal material, for example,aluminum (Al), copper (Cu), nickel (Ni) and stainless steel.

The recess-provided sheet piece 300A and the platy sheet piece 300B areeach formed of, for example, a rectangular laminated film obtained bysticking a nylon film, an aluminum foil and a polyethylene film in thisorder as described previously, and the peripheral parts 36A and 36B ofthe both sheet pieces are superimposed and heat sealed to form thesealing part 38. Also, the portion including the bending part 34 in thesealing part 38 has the thick-walled part 40. Furthermore, the sealant24 for preventing penetration of the air is inserted between therecess-provided sheet piece 300A and the platy sheet piece 300B andbetween the positive electrode terminal 22 a and the negative electrodeterminal 22 b.

FIG. 8 is a schematic cross-sectional view along a VIII-VIII line of thebattery element 20 shown in FIG. 7.

In FIG. 8, in the battery element 20, a positive electrode 210 and anegative electrode 220 are disposed opposing to each other and wound viaa polymeric support layer (as described later) 230 which holds anon-aqueous electrolytic solution and a separator 240; and an outermostperipheral part thereof is protected by a protective tape 250.

As shown in FIG. 8, for example, the positive electrode 210 has astructure in which a positive electrode active material layer 210B iscoated on the both surfaces or one surface of a positive electrodecollector 210A having a pair of opposing surfaces. The positiveelectrode collector 210A includes a portion where the positive electrodeactive material layer 210B is exposed without being coated, in one endin the longitudinal direction, and the positive electrode terminal 22 ais installed in this exposed portion.

The positive electrode collector 210A is constituted of a metal foil,for example, an aluminum foil, a nickel foil and a stainless steel foil.

The positive electrode active material layer 210B contains, as apositive electrode active material, any one kind or two or more kinds ofa positive electrode material capable of intercalating anddeintercalating a lithium ion and may contain a conductive agent and abinder as the need arises.

Examples of the positive electrode material capable of intercalating anddeintercalating a lithium ion include lithium-free chalcogen compounds(especially, layered compounds and spinel type compounds), for example,sulfur (S), iron disulfide (FeS₂), titanium disulfide (TiS₂), molybdenumdisulfide (MoS₂), niobium diselenide (NbSe₂), vanadium oxide (V₂O₅),titanium dioxide (TiO₂) and manganese dioxide (MnO₂); lithium-containingcompounds containing lithium therein; and conductive polymer compounds,for example, polyaniline, polythiophene, polyacetylene and polypyrrole.

Of these, lithium-containing compounds are preferable because theyinclude ones capable of obtaining high voltage and high energy density.Examples of such a lithium-containing compound include complex oxidescontaining lithium and a transition metal element; and phosphatecompounds containing lithium and a transition metal. From the viewpointof obtaining a higher voltage, those containing cobalt (Co), nickel(Ni), manganese (Mn), iron (Fe), copper (Cu), zinc (Zn), chromium (Cr),vanadium (V), titanium (Ti) or an arbitrary mixture thereof arepreferable.

Such a lithium-containing compound is representatively represented bythe following general formula (1) or (2).Li_(x)M^(I)O₂  (1)Li_(y)M^(II)PO₄  (2)

In the foregoing formulae, M^(I) and M^(II) each represents one or morekinds of a transition metal element; and values of x and y varydepending upon the charge-discharge state of the battery and are usuallysatisfied with 0.05≦x≦1.10 and 0.05≦y≦1.10, respectively. The compoundof the formula (1) generally has a layered structure; and the compoundof the formula (2) generally has an olivine structure.

Also, specific examples of the complex oxide containing lithium and atransition metal element include a lithium cobalt complex oxide(Li_(x)CoO₂), a lithium nickel complex oxide (Li_(x)NiO₂), lithiumnickel cobalt complex oxide (Li_(x)Ni_(1-z)Co_(z)O₂) (0<z<1)) and alithium manganese complex oxide having a spinel structure (LiMn₂O₄).

Specific examples of the phosphate compound containing lithium and atransition metal element include a lithium iron phosphate compoundhaving an olivine structure (LiFePO₄) and a lithium iron manganesephosphate compound (LiFe_(1-v)Mn_(v)PO₄ (v<1)).

In these complex oxides, for the purpose of stabilizing the structure orthe like, ones in which a part of the transition metal is substitutedwith Al, Mg or other transition metal element or contained in a crystalgrain boundary and ones in which a part of oxygen is substituted withfluorine, etc, can be exemplified. Furthermore, at least a part of thesurface of the positive electrode active material may be coated withother positive electrode active material. Also, a mixture of pluralkinds of materials may be used as the positive electrode activematerial.

On the other hand, likewise the positive electrode 210, the negativeelectrode 220 has, for example, a structure in which a negativeelectrode active material layer 220B is provided on the both surfaces orone surface of a negative electrode collector 220A having a pair ofopposing surfaces. The negative electrode collector 220A has a portionwhich is exposed without being provided with the negative electrodeactive material layer 220B in one end in the longitudinal directionthereof, and the negative electrode terminal 22 b is installed in thisexposed portion.

The negative electrode collector 220A is constituted of a metal foil,for example, a copper foil, a nickel foil and a stainless steel foil.

The negative electrode active material layer 220B contains, as anegative electrode active material, any one kind or two or more kinds ofa negative electrode material capable of intercalating anddeintercalating a lithium ion and metallic lithium and may contain aconductive agent and a binder as the need arises.

Examples of the negative electrode material capable of intercalating anddeintercalating lithium include carbon materials, metal oxides andpolymer compounds. Examples of the carbon material include hardlygraphitized carbon materials, artificial graphite materials and graphitebased materials. More specific examples thereof include pyrolyticcarbons, cokes, graphites, vitreous carbons, organic polymer compoundburned materials, carbon fibers, active carbon and carbon black.

Of these, examples of the coke include pitch coke, needle coke andpetroleum coke. The organic polymer compound burned material as referredto herein is a material obtained through carbonization by burning apolymer material, for example, phenol resins and furan resins at anappropriate temperature. Also, examples of the metal oxide include ironoxide, ruthenium oxide and molybdenum oxide; and examples of the polymermaterial include polyacetylene and polypyrrole.

Furthermore, examples of the negative electrode material capable ofintercalating and deintercalating lithium include materials containing,as a constitutional element, at least one of metal elements andsemi-metal elements capable of forming an alloy together with lithium.This negative electrode material may be a single body, an alloy or acompound of a metal element or a semi-metal element. Also, one havingone or two or more kinds of a phase in at least a part thereof may beused.

In an embodiment, the alloy also includes an alloy containing one or twoor more kinds of a metal element and one or two or more kinds of asemi-metal element in addition to alloys composed of two or more kindsof a metal element. Also, the alloy may contain a non-metal element.Examples of its texture include a solid solution, a eutectic (eutecticmixture), an intermetallic compound and one in which two or more kindsthereof coexist.

Examples of such a metal element or semi-metal element include tin (Sn),lead (Pb), aluminum, indium (In), silicon (Si), zinc (Zn), antimony(Sb), bismuth (Bi), gallium (Ga), germanium (Ge), arsenic (As), silver(Ag), hafnium (Hf), zirconium (Zr) and yttrium (Y).

Above all, a metal element or a semi-metal element belonging to theGroup 14 of the long form of the periodic table is preferable; andsilicon or tin is especially preferable. This is because silicon and tinhave a large ability to intercalate and deintercalate lithium and areable to obtain a high energy density.

Examples of alloys of tin include alloys containing, as a secondconstitutional element other than tin, at least one member selected fromthe group consisting of silicon, magnesium (Mg), nickel, copper, iron,cobalt, manganese, zinc, indium, silver, titanium (Ti), germanium,bismuth, antimony and chromium (Cr).

Examples of alloys of silicon include alloys containing, as a secondconstitutional element other than silicon, at least one member selectedfrom the group consisting of tin, magnesium, nickel, copper, iron,cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth,antimony and chromium.

Examples of compounds of tin or silicon include compounds containingoxygen (O) or carbon (C), and these compounds may contain the foregoingsecond constitutional element in addition to tin or silicon.

Next, the polymeric support layer 230 has ion conductivity and is ableto hold a non-aqueous electrolytic solution therein. In the embodimentas shown in FIG. 8, this polymeric support layer 230 comes into intimatecontact with or adheres to the separator 240. The polymeric supportlayer 230 may come into intimate contact with or adhere to the separatorand the electrode as in the separator 240 and the positive electrode 210or the separator 240 and the negative electrode 220. Alternatively, thepolymeric support layer 230 may not come into intimate contact with oradhere to the separator but come into intimate contact with or adhere toeither one or both of the positive electrode 210 and the negativeelectrode 220.

It is meant by the terms “intimate contact” as referred to herein thatthe polymeric support layer 230 comes into contact with the separator240 or the positive electrode 210 or the negative electrode 220 closelyto an extent that they do not relatively move each other unless aprescribed force is added.

When the polymeric support layer 230 and the separator 240, or thepolymeric support layer 230 and the positive electrode or negativeelectrode come into intimate contact with or adhere to each other, thepolymeric support layer 230 holds a non-aqueous electrolytic solutiontherein and becomes a gel non-aqueous electrolyte layer, whereby thepositive electrode 210 or the negative electrode 220 and the separator240 adhere to each other via this non-aqueous electrolyte layer.

The degree of this adhesion is preferably a degree such that, forexample, a peel strength between the separator and the exposed portionof the positive electrode 210 or the negative electrode 220 where theactive material layer is not provided, but the collector is exposed is 5mN/mm or more. The peel strength is an average value of the forcerequired to peel the collector disposed on a supporting table from theseparator while pulling at a rate of 10 cm/min in the 180° directionwithin a time period of from 6 seconds to 25 seconds after start of thepulling.

By such intimate contact or adhesion, in the non-aqueous electrodesecondary battery according to an embodiment, an excess of thenon-aqueous electrolytic solution which does not substantiallycontribute to a battery reaction can be reduced, and the non-aqueouselectrolytic solution is efficiently fed into the surroundings of theelectrode active material. Accordingly, the non-aqueous electrolytesecondary battery according to an embodiment exhibits desirable cyclecharacteristics even with a smaller amount of the non-aqueouselectrolytic solution than that of the related art. Also, since theamount of the non-aqueous electrolytic solution to be used is small, theresistance to liquid leakage is desirable.

The polymeric support which constitutes the foregoing polymeric supportlayer is not particularly limited so far as it holds the non-aqueouselectrolytic solution therein, thereby exhibiting ion conductivity.Examples thereof include acrylonitrile based polymers having acopolymerization amount of acrylonitrile of 50% by mass or more, andespecially 80% by mass or more, aromatic polyamides,acrylonitrile/butadiene copolymers, acrylic polymers composed of anacrylate or methacrylate homopolymer or copolymer, acrylamide basedpolymers, fluorine-containing polymers of vinylidene fluoride, etc.,polysulfones and polyarylsulfones. In particular, a polymer having acopolymerization amount of acrylonitrile of 50% by mass or more has a CNgroup in a side chain thereof, and thus, it is able to form a polymericgel electrolyte with high dielectric constant and high ion conductivity.

In order to enhance the supporting properties of the non-aqueouselectrolytic solution relative to such a polymer or enhance the ionconductivity of the polymeric gel electrolyte from such a polymer,copolymers obtained by copolymerizing acrylonitrile with a vinylcarboxylic acid (for example, acrylic acid, methacrylic acid anditaconic acid), acrylamide, methacrylsufonic acid, a hydroxyalkyleneglycol (meth)acrylate, an alkoxyalkylene glycol (meth)acrylate, vinylchloride, vinylidene chloride, vinyl acetate, a (meth)acrylate of everysort, etc. in a proportion of preferably not more than 50% by mass, andespecially not more than 20% by mass can be used.

Also, the aromatic polyamide is a high heat-resistant polymer. Thus, inthe case where a polymeric gel electrolyte which is required to havehigh heat resistance as in automobile batteries is required, thearomatic polyamide is a preferred polymer compound. A polymer having acrosslinking structure which is obtained through copolymerization withbutadiene, etc. can also be used.

In particular, polymers containing, as a constitutional component,vinylidene fluoride, namely homopolymers, copolymers and multi-componentcopolymers are preferable as the polymeric support. Specific examplesthereof include polyvinylidene fluoride (PVdF), a polyvinylidenefluoride-hexafluoropropylene copolymer (PVdF-HFP) and a polyvinylidenefluoride-hexafluoropropylene-chlorotrifluoroethylene copolymer(PVdF-HEP-CTFE).

Next, the separator 240 is usually configured to have an insulating thinmembrane having high ion permeability and predetermined mechanicalstrength, such as a porous membrane composed of a polyolefin based resinor a porous membrane composed of an inorganic material such as anon-woven fabric made of a ceramic, or the like. However, in thenon-aqueous electrolyte secondary battery according to the presentembodiment, it is preferable that the separator 240 is configured tohave a porous membrane containing polyethylene as a main component andcontaining not more than 10% by mass of polypropylene.

Here, in the separator in which polyethylene and polypropylene coexist,since a melting point of polypropylene is higher than that ofpolyethylene, the start temperature of heat shrinkage can be shifted toa higher temperature side. Inversely, since a shutdownfunction-revealing temperature of polypropylene is high, the batterytemperature at the time of overcharge or internal short circuit easilybecomes high, and therefore, thermorunaway is easily caused.

According to an embodiment, by making a mixing ratio of polyethylene andpolypropylene fall within the foregoing range, the start temperature ofheat shrinkage can be increased while keeping the shutdownfunction-revealing temperature low.

While the start temperature of heat shrinkage is low as compared withthe case of 100% by mass of polypropylene, according to an embodiment,the separator and the electrode firmly adhere to each other by theforegoing polymeric support, and therefore, it is possible to adequatelycontrol the heat shrinkage. Furthermore, according to such a structurewhere the polymeric support is arranged, since the separator itself canbe made thin, the energy density of the battery can be kept high.

Also, as constitutional components of the foregoing separator, it ispreferable to choose polyethylene having a melting point of from about130 to 140° C. or polypropylene having a melting point of from about 160to 170° C.

When a material having an excessively low melting point is contained asthe constitutional component of the separator, a temperature at whichthe separator fuses is low so that the useful temperature becomes low.On the other hand, when a material having an excessively high meltingpoint is contained as the constitutional component of the separator, atemperature at which the separator reveals the shutdown function is highso that thermorunaway is possibly caused, whereby there may be the casewhere it is difficult to secure the safety. Also, when there is adifference in melting point of 20° C. or more in the pluralconstitutional components, the functions including both shutdown andavoidance of the heat shrinkage can be sufficiently obtained.

A thickness of the separator is preferably from 5 to 20 μm.

Next, the non-aqueous electrolytic solution may be any solutioncontaining an electrolyte salt and a non-aqueous solvent.

Here, the electrolyte salt may be any salt capable generating an ionupon being dissolved or dispersed in a non-aqueous solvent as describedlater. Though lithium hexafluorophosphate (LiPF₆) can be favorably used,needless to say, the electrolyte salt is not limited thereto.

That is, inorganic lithium salts, for example, lithium tetrafluoroborate(LiBF₄), lithium hexafluoroarsenate (LiAsF₆), lithiumhexafluoroantimonate (LiSbF₆), lithium perchlorate (LiClO₄) and lithiumtetrachloroaluminate (LiAlCl₄); lithium salts of aperfluoroalkanesulfonate derivative, for example, lithiumtrifluoromethanesulfonate (LiCF₃SO₃), lithiumbis(trifluoromethanesulfone)imide (LiN(CF₃SO₂)₂), lithiumbis(pentafluoromethanesulfone)imide (LiN(C₂F₅SO₂)₂) and lithiumtris-(trifluoromethanesulfone)methide (LiC(CF₃SO₂)₃) can be used. Thesesalts can be used singly or in combinations of two or more kindsthereof.

The content of such an electrolyte salt is preferably from 5 to 25% bymass. When the content of such an electrolyte salt is less than 5% bymass, there is a concern that sufficient conductivity is not obtainable.On the other hand, when it exceeds 25% by mass, there is a concern thatthe viscosity excessively increases.

Also, examples of the non-aqueous solvent include varioushigh-dielectric solvents and low-viscosity solvents.

Ethylene carbonate or propylene carbonate or the like can be favorablyused as the high-dielectric solvent, but the high-dielectric solvent isnot limited thereto. Other examples of the high-dielectric solventinclude cyclic carbonates, for example, butylene carbonate, vinylenecarbonate, 4-fluoro-1,3-dioxolan-2-one (fluoroethylene carbonate),4-chloro-1,3-dioxolan-2-one (chloroethylene carbonate) andtrifluoromethylethylene carbonate.

Also, in place of, or in addition to, the cyclic carbonate, a lactone,for example, γ-butyrolactone and γ-valerolactone, a lactam, for example,N-methylpyrrolidone, a cyclic carbamic ester, for example,N-methyloxazolidinone, a sulfone compound, for example, tetramethylenesulfone or the like can be used as the high-dielectric solvent.

On the other hand, diethyl carbonate can be favorably used as thelow-viscosity solvent. Besides, chain carbonates, for example, dimethylcarbonate, ethyl methyl carbonate and methyl propyl carbonate; chaincarboxylic esters, for example, methyl acetate, ethyl acetate, methylpropionate, ethyl propionate, methyl butyrate, methyl isobutyrate,methyl trimethylacetate and ethyl trimethylacetate; chain amides, forexample, N,N-dimethylacetamide; chain carbamic esters, for example,methyl N,N-diethylcarbamate and ethyl N,N-diethylcarbamate; and ethers,for example, 1,2-dimethoxyethane, tetrahydrofuran, tetrahydropyran and1,3-dioxolane.

As the non-aqueous electrolytic solution to be used in the non-aqueouselectrolyte secondary battery according to an embodiment, the foregoinghigh-dielectric solvent and low-viscosity solvent can be used singly orin admixture of two or more kinds thereof at any desired mixing ratio.Preferably, the non-aqueous electrolytic solution contains from 20 to50% by mass of a cyclic carbonate and from 50 to 80% by mass of alow-viscosity solvent (low-viscosity non-aqueous solvent). Inparticular, a chain carbonate having a boiling point of not higher than130° C. is desirably used as the low-viscosity solvent. By using such anon-aqueous electrolytic solution, the polymeric support can befavorably swollen with a small amount of the non-aqueous electrolyticsolution, and it is possible to devise to make both suppression ofswelling or prevention of the leakage of the battery and highconductivity much more compatible with each other.

When the ratio of the cyclic carbonate to the low-viscosity solventfalls outside the foregoing range, there is a concern that theconductivity of the electrolytic solution is lowered, and the cyclecharacteristics are lowered.

Examples of the chain carbonate having a boiling point of not higherthan 130° C. include dimethyl carbonate, ethyl methyl carbonate anddiethyl carbonate.

Also, what a halogen atom-containing cyclic carbonic ester derivative iscontained as the foregoing cyclic carbonate in the non-aqueouselectrolytic solution is more preferable because the cycliccharacteristics are improved.

Examples of such a cyclic carbonic ester derivative include4-fluoro-1,3-dioxolan-2-one and 4-chloro-1,3-dioxolan-2-one. Thesecyclic carbonic ester derivatives can be used singly or in combinations.

The content of the cyclic carbonic ester derivative is preferably from0.5 to 2% by mass. When the content of the cyclic carbonic esterderivative is too low, an effect for enhancing the cycliccharacteristics is small, whereas when it is too high, there is aconcern that swelling at the time of high-temperature storage becomeslarge.

According to an embodiment, since the amount of the non-aqueouselectrolytic solution existing between the polymeric support layer andthe separator, the positive electrode or the negative electrode withoutbeing supported by any of them is low, even when the low-viscositysolvent having a low boiling point is used in an amount of 50% by massor more, the swelling is suppressed to a low level.

In the non-aqueous electrolyte secondary battery according to anembodiment as described previously, the amount of the non-aqueouselectrolytic solution existing within the battery, typically the pouringamount of the non-aqueous electrolytic solution is preferably from 0.14to 0.35 g per cm³ of the volume of this non-aqueous electrolytesecondary battery.

When the pouring amount of the non-aqueous electrolytic solution is lessthan 0.14 g per cm³ of the volume of the battery, there is a concernthat expected battery performances, specifically expected initialcharge-discharge capacity and capacity retention rate cannot berealized, whereby when it exceeds 0.35 g, there is a concern that theresistance to liquid leakage is lowered.

Here, the pouring amount within the battery is, for example, measured bya method as described below.

First of all, a weight of the battery is measured; and subsequently, thebattery element is taken out and then disassembled into the positiveelectrode, the negative electrode and the separator. Thereafter, thepositive electrode, the negative electrode, the separator and theexterior member are immersed in a dimethyl carbonate solution for 2days; and after filtration, vacuum drying is carried out for 3 days. Avalue obtained by subtracting the weight after vacuum drying from theinitial weight is defined as the pouring amount.

Also, in the non-aqueous electrolyte secondary battery according to thepresent embodiment, it is preferable that a ratio (MO/MA) of the amountMO of the non-aqueous electrolytic solution existing between the batteryelement 20 and the exterior member 300 for a battery element to theamount MA of the non-aqueous electrolytic solution existing inside theexterior member 300 for a battery element is not more than 0.04.

When the thus defined MO/MA exceeds 0.04, there is a concern thatswelling of the battery at the time of high-temperature storage cannotbe sufficiently suppressed. Also, it is preferable that the MO/MA valueis small as far as possible. Most desirably, the MO/MA value is 0.However, even when it is not more than 0.03, a more remarkable effectfor suppressing swelling can be obtained.

Here, the amount MA of the non-aqueous electrolytic solution existing ininside the exterior member for a battery element, namely within thenon-aqueous electrolyte secondary battery may be, for example, measuredand calculated in the following method.

First of all, a mass of the battery is measured; and subsequently, thebattery element is taken out and then disassembled into the positiveelectrode, the negative electrode and the separator. Subsequently, thepositive electrode, the negative electrode, the separator and theexterior member for a battery element are immersed in a rinse liquidsuch as dimethyl carbonate for 2 days; and after filtration, vacuumdrying is carried out for 3 days. Thereafter, a mass of the batteryafter vacuum drying is measured, and the mass of the battery aftervacuum drying is subtracted from the initial mass of the battery,thereby determining MA.

On the other hand, the amount MO of the non-aqueous electrolyticsolution existing between the battery element and the exterior memberfor a battery element, namely existing within the battery and outsidethe battery element may be, for example, measured and calculated in thefollowing method.

First of all, a mass of the battery is measured, and the battery elementis then taken out. Subsequently, the thus taken out battery element isinterposed by a raw material capable of absorbing the non-aqueouselectrolytic solution therein, for example, cloths, and all of thenon-aqueous electrolytic solutions which have oozed out upon applicationof a load of 10 kPa are wiped off. Also, the exterior member from whichthe battery element has been taken out is immersed in a rinse liquidsuch as dimethyl carbonate and then dried. Thereafter, a total mass ofthe exterior member and the battery element having been subjected to awiping-off treatment is measured, and the total mass of the exteriorbody and the electrode body after the wiping-off treatment is subtractedfrom the initial mass of the battery, thereby determining MO.

Next, one example of the manufacturing method of the foregoing batteryelement is described.

First of all, the positive electrode 210 is prepared. For example, inthe case of using a granular positive electrode active material, apositive electrode active material and optionally, a conductive agentand a binder are mixed to prepare a positive electrode mixture, which isthen dispersed in a dispersion medium, for example,N-methyl-2-pyrrolidone to prepare a positive electrode mixture slurry.

Subsequently, this positive electrode mixture slurry is coated on thepositive electrode collector 210A and dried, and then compression moldedto form the positive electrode active material layer 210B.

Also, the negative electrode 220 is prepared. For example, in the caseof using a granular negative electrode active material, a negativeelectrode active material and optionally, a conductive agent and abinder are mixed to prepare a negative electrode mixture, which is thendispersed in a dispersion medium such as N-methyl-2-pyrrolidone toprepare a negative electrode mixture slurry. Thereafter, this negativeelectrode mixture slurry is coated on the negative electrode collector220A and dried, and then compression molded to form the negativeelectrode active material layer 220B.

The polymeric support layer 230 is then formed on the separator 240.Examples of the technique for forming the polymeric support layer 230 onthe separator 240 include a technique of coating a polymericsupport-containing solution on the surface of the separator 240 andremoving the solvent; and a technique of affixing a separately preparedpolymeric support layer on the surface of the separator 240.

Examples of the technique for coating the polymeric support-containingsolution on the surface of the separator 240 include a technique ofimmersing the separator in the polymeric support-containing solution; atechnique of feeding and coating the solution by means of a T-dieextrusion process or the like; and a technique of coating the solutionon the surface of a base material by a spraying process or with a rollcoater, a knife coater, or the like.

Examples of the technique of a desolvation treatment for removing thesolvent include a technique of removing the solvent by drying; atechnique of immersing the coated layer in a poor solvent of thepolymeric support to remove the solvent by extraction and then dryingand removing the poor solvent; and a combination of these techniques.

As the technique of affixing the separately prepared polymeric supportlayer to the surface of the separator 240, the adhesion can be achievedby using an adhesive. In that case, however, the adhesive must beadequately chosen according to the type of the electrolytic solution tobe used (for example, an acid, an alkali, an organic solvent, etc.), andattention may be paid not so as to generate clogging.

Also, examples of technique for allowing the prepared polymeric supportlayer to come into intimate contact with the separator include heatfusion at a temperature of the gel transition point or higher. Inparticular, heat fusion while applying a pressure, for example, hot rollcompression is preferable.

Subsequently, the positive electrode terminal 22 a is installed in thepositive electrode 210, and the negative electrode terminal 22 b is alsoinstalled in the negative electrode 220. Thereafter, the separator 240provided with the polymeric support layer 230, the positive electrode210, another separator 240 of the same type and the negative electrode220 are successively laminated and wound. The protective tape 250 isadhered onto the outermost peripheral part to form a wound electrodebody.

Thereafter, an electrolyte salt such as lithium hexafluorophosphate anda non-aqueous electrolytic solution containing a non-aqueous solventsuch as ethylene carbonate are prepared and poured into the inside ofthe wound electrode body, thereby holding the non-aqueous electrolyticsolution in the polymeric support layer 230 to form an electrolyte.There is thus completed the battery element 20.

For example, pouring of the non-aqueous electrolytic solution can alsobe achieved in the state that the superimposed recess-provided sheetpiece 300A and platy sheet piece 300B are sealed with each other exceptfor one side (for example, a side parallel to the bending part 34),thereby forming a bag, into which is then housed the wound electrodebody before pouring the electrolytic solution. By employing thistechnique, a precursor which will be a raw material for forming thepolymeric support and the solvent can be removed in advance so that sucha material or solvent does not remain within the electrolyte. Also, thestep of forming the polymeric support can be favorably controlled. Forthat reason, it is possible to make the polymeric support layer comeinto intimate contact with the separator, the positive electrode or thenegative electrode.

In the non-aqueous electrolyte secondary battery as describedpreviously, when charged, a lithium ion is deintercalated from thepositive electrode active material layer 210B and intercalated in thenegative electrode active material layer 220B via the non-aqueouselectrolytic solution held in the polymeric support layer 230. Whendischarged, a lithium ion is deintercalated from the negative electrodeactive material layer 220B and intercalated in the positive electrodeactive material layer 210B via the polymeric support layer 230 and thenon-aqueous electrolytic solution.

Here, in the exterior member for a battery element to be included in theforegoing non-aqueous electrolyte secondary battery, the thick-walledpart is formed in the bending part which is likely influenced especiallyby a heat stress, chemical changes of a resin layer and an adhesivelayer, etc. during heat sealing for hermetically sealing the batteryelement. Thus, the exterior member for a battery element is hardlydamaged by such influences and has excellent hermetic sealingproperties.

Also, the thick-walled part is favorably formed by a lower pressure thanthat in other sealing part. However, since the area which is occupied bythe thick-walled part is relatively small, there is brought an advantagethat swelling of the battery to be caused due to penetration of watergenerated in the case of, for example, using an exterior member for abattery element in which all other sealing parts are formed under a lowpressure can be avoided.

EXAMPLES

The present application according to an embodiment is hereunderdescribed below in more detail with reference to the following Examplesand Comparative Examples while referring to the accompanying drawings.

Example 1

First of all, cobalt carbonate (CoCO₃) was mixed in a proportion of 1mole per 0.5 moles of lithium carbonate (Li₂CO₃), and the mixture wasburned in air at 900° C. for 5 hours, thereby obtaining a lithium cobaltcomplex oxide (LiCoO₂) as a positive electrode active material.

Subsequently, 85 parts by mass of the obtained lithium cobalt complexoxide, 5 parts by mass of graphite as a conductive agent and 10 parts bymass of polyvinylidene fluoride as a binder were mixed to prepare apositive electrode mixture, which was then dispersed inN-methyl-2-pyrrolidone as a dispersion medium to form a positiveelectrode mixture slurry. Subsequently, this positive electrode mixtureslurry was uniformly coated on the both surfaces of the positiveelectrode collector 210A composed of an aluminum foil and having athickness of 20 μm, dried and then compression molded by a roll press toform the positive electrode active material layer 210B. There was thusprepared the positive electrode 210. Thereafter, the positive electrodeterminal 22 a was installed in the positive electrode 210.

On the other hand, a pulverized graphite powder was prepared as anegative electrode active material. 90 parts by mass of this graphitepowder and 10 parts by mass of polyvinylidene fluoride as a binder weremixed to prepare a negative electrode mixture, which was then dispersedin N-methyl-2-pyrrolidone as a dispersion medium to form a negativeelectrode mixture slurry.

Subsequently, this negative electrode mixture slurry was uniformlycoated on the both surfaces of the negative electrode collector 220Acomposed of a copper foil and having a thickness of 15 μm, dried andthen compression molded by a roll press to form the negative electrodeactive material layer 220B. There was thus prepared the negativeelectrode 220. Subsequently, the negative electrode terminal 22 b wasinstalled in the negative electrode 220.

Also, polyvinylidene fluoride was used as a polymer compound to be usedfor the polymeric support layer 230. A solution of the subject polymerprepared by dissolving it in an N-methyl-2-pyrrolidone solution in anamount of 12 parts by mass was coated on the both surface of theseparator 240 composed of a microporous film and having a thickness of12 μm by a coating unit. This coated film was immersed in deionizedwater and then dried to form the polymeric support layer 230 having athickness of 5 μm on the separator 240.

The thus prepared positive electrode 210 and negative electrode 220 werebrought into intimate contact with each other via the separator 240having the polymeric support layer 230 formed thereon and then wound inthe longitudinal direction, and the protective tape 250 was stuck on theoutermost periphery, thereby preparing the battery element 20.

Furthermore, the prepared battery element 20 was housed in the recess 32of the recess-provided sheet piece 300A made of a laminated sheet.Subsequently, the bending part 34 was folded to superimpose therecess-provided sheet piece 300A and the platy sheet piece 300B.Thereafter, the peripheral part 36 of the two long sides was heat sealedusing the level difference-provided heat bar as shown in FIG. 5C,thereby forming the sealing part 38 and the thick-walled part 40. Therewas thus obtained the exterior member 300 for a battery element in a bagform.

The sealing part 38 had a thickness of 180 μm, and the thick-walled part40 had a thickness of 240 μm. Also, the length of the thick-walled partin the long side direction was 5% relative to the length of the longside of the exterior member for a battery element.

A moistureproof aluminum laminated film prepared by laminating a 25μm-thick nylon film, a 40 μm-thickness aluminum foil and a 30 μm-thickpolypropylene film in this order from the outermost layer was used asthe laminated sheet. The thickness of the thick-walled part was thickerthan a total thickness of the stuck two laminated sheets. It may beconsidered that this was caused due to the fact that the polypropylenefilm as a sealing resin flowed into the thick-walled part at the time ofheat sealing.

Subsequently, an electrolytic solution was poured into the exteriormember 300 for a battery element in a bag form having the batteryelement 20 housed therein, and the peripheral part of the remaining oneside was heat sealed under a reduced pressure using the heater bar in aplaty shape, thereby achieving hermetic sealing.

An electrolytic solution prepared by dissolving 1.2 moles/L of lithiumhexafluorophosphate in a mixed solvent of ethylene carbonate anddiethylene carbonate in a mass ratio of ethylene carbonate to diethylenecarbonate of 3/7 was used.

Thereafter, the obtained hermetically sealed body was interposed bysteel plates and heated at 70° C. for 3 minutes, thereby allowing theseparator 240 to adhere to each of the positive electrode 210 and thenegative electrode 220 via the polymeric support layer 230. There wasthus obtained a non-aqueous electrolyte secondary battery of thisExample.

Comparative Example 1

A non-aqueous electrolyte secondary battery of this Comparative Examplewas obtained by repeating the same operations as in Example 1, exceptfor changing the heater bar for heat sealing the long side to the heaterbar in a platy shape as shown in FIG. 5A. The sealing part had athickness of 180 μm.

<Leakage Test of the Contents of Battery>

Five samples for each of the secondary batteries of Example 1 andComparative Example 1 were prepared and provided for this test.

Each of the secondary battery samples was charged and then stored for 20days in a vacuum furnace (vacuum condition: not more than −0.1 MPa(gauge pressure), temperature within the furnace: 50° C.), followed bytaking out from the vacuum furnace. The leakage of the contents of thebattery from the bending part 34 of the exterior member 30 for a batteryelement was visually observed.

As a result, as to the secondary battery of Example 1, the leakage wasnot observed with respect to all of the five samples. On the other hand,the leakage was confirmed in four of the five samples with respect tothe secondary battery of Comparative Example 1.

It has been noted from these results that the hermetic sealingproperties of the secondary battery of the application is markedlyenhanced as compared with those of the related-art product.

While the present application has been described in detail with respectto some embodiments and working examples, the present application isnever limited to these embodiments and working examples, and variouschanges and modifications can be made therein without departing from thespirit and scope thereof.

For example, the polymeric support layer 230 is not an essential elementand may be omitted.

The present application contains subject matter related to thatdisclosed in Japanese Priority Patent Application JP 2008-144781 filedin Japan Patent Office on Jun. 2, 2008, the entire contents of which ishereby incorporated by reference.

It should be understood that various changes and modifications to thepresently preferred embodiments described herein will be apparent tothose skilled in the art. Such changes and modifications can be madewithout departing from the spirit and scope and without diminishing itsintended advantages. It is therefore intended that such changes andmodifications be covered by the appended claims.

The application is claimed as follows:
 1. A non-aqueous electrolytesecondary battery comprising: a battery element having a positiveelectrode, a negative electrode and a separator; and an exterior memberfor the battery element including: a first laminate layer; a secondlaminate layer; a bending part for partitioning the first laminate layerand the second laminate layer from each other; a sealing part which isformed by a peripheral part of the first laminate layer in contact witha peripheral part of the second laminate layer and which seals thebattery element; and a thick-walled part that is a portion of thesealing part and includes at least a part of the bending part, whereinthe thick-walled part has a greater thickness in a thickness directionof the battery element than a thickness of a portion of the sealing partother than the thick-walled part, and wherein the thickness direction ofthe battery element corresponds to a stacking direction of the batteryelement.
 2. The non-aqueous electrolyte secondary battery according toclaim 1, wherein the thick-walled part is formed by heat pressing theportion of the sealing part forming the thick-walled part at a lowerpressure than the portion of the sealing part other than thethick-walled part.
 3. The non-aqueous electrolyte secondary batteryaccording to claim 1, wherein a thickest portion of the thick-walledpart has a thickness of from 1.2 to 3 times that of the portion of thesealing part other than the thick-walled part.
 4. The non-aqueouselectrolyte secondary battery according to claim 1, wherein a length ina long side direction of the thick-walled part is not more than 80%relative to a length of a long side of the exterior member.
 5. Thenon-aqueous electrolyte secondary battery according to claim 1, wherein:at least one of the first laminate layer and the second laminate layerincludes a recess; and the battery element is housed in a space formedby the recess.
 6. The non-aqueous electrolyte secondary batteryaccording to claim 1, wherein at least one of the first laminate layerand the second laminate layer comprises an exterior layer and a sealantlayer.
 7. The non-aqueous electrolyte secondary battery according toclaim 1, wherein the first laminate layer and the second laminate layerare formed from a single laminated sheet.
 8. The non-aqueous electrolytesecondary battery according to claim 1, wherein the positive electrodeand the negative electrode are wound with the separator therebetween. 9.The non-aqueous electrolyte secondary battery according to claim 1,wherein the positive electrode and the negative electrode are wound viaa polymeric support layer that holds a non-aqueous electrolytic solutionand the separator.
 10. The non-aqueous electrolyte secondary batteryaccording to claim 9, wherein at least one of the positive electrode andthe negative electrode are adhered to the separator via the polymericsupport layer.